Reaction Steps
Oxidation of epihippuristanol (10) to give epihippuristanol 11-one (13) and epihippuristanol 3,11-dione (14). Epihippuristanol (10, 31.4 mg) was oxidized in the same fashion as described above for hippuristanol (1). The crude product was separated by TLC (CHCl3/EtOAc, 1:1, v/v) to give 12.6 mg of epihippuristanol 11-one (13, 40%) and 14.0 mg of epihippuristanol 3,11-dione (14, 45%). Epihippuristanol 3,11-dione (14). white crystals, mp 226-229° C.; 1H NMR (CDCl3) δ 4.48 (brq, J=7.0 Hz, 1H), 2.82 (ddd, J=13, 6.5, 2 Hz, 1H), 2.57 (d, J=12 Hz, 1H), 2.45 (dt, J=6.5, 14 Hz, 1H), 1.30 (s, 3H), 1.28 (s, 3H), 1.22 (s, 3H), 1.08 (s, 3H), 0.98 (s, 3H), 0.94 (d, J=7 Hz, 3H); 13C NMR (CDCl3) δ 211.4, 209.9, 118.6, 84.5, 81.9, 79.0, 64.1, 63.2, 58.2, 55.8, 47.0, 45.9, 44.3, 41.0, 39.6, 38.0, 37.1, 35.8 (2C), 35.3, 32.3, 31.5, 29.0, 28.2, 26.0, 23.0, 17.6, 14.0, 11.1; IR (KBr) 3450, 1700 cm−1; EIMS m/z 458 (M+, 6), 443 (16), 400 (7), 330 (32), 315 (100%).
